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Copper(II) hydrazone complexes with different nuclearities and geometries: synthetic methods and ligand substituent effects

A series of copper(II) complexes with 4- hydroxybenzhydrazone-related ligands was synthesized by using various methods, including conventional solution-based method, solvothermal route and electrochemical synthesis. The complexes can be classified as mononuclear [Cu(L3OMe)(py)] (2py), dinuclear [Cu2(LH)2(py)2] (1py), [Cu2(LH)2] (1 and 1β), [Cu2(LH)2(py)2] (1py), [Cu2(L4OMe)2(py)2] (3py), [Cu2(L4OMe )2] (3), [Cu2(L4OMe )2(MeOH)2] (3MeOH), [Cu2(L4OMe)2(EtOH)2] (3EtOH), cubane tetranuclear [Cu4(L3OMe)4]∙xsolv (2MeOH and 2EtOH), or polynuclear [Cu(LH)(py)]n (1py*), where LH = 2- oxybenzaldehyde 4- hydroxybenzhydrazonato, L3OMe = 3-methoxy-2- oxybenzaldehyde 4- hydroxybenzhydrazonato, and L4OMe = 4-methoxy-2- oxybenzaldehyde 4- hydroxybenzhydrazonato ligands. The presented study indicates that complexes having different nuclearities or/and geometries can be achieved by changing synthetic conditions and methods. Thermally induced structural transformations of the dinuclear complexes under solvent-free conditions were also investigated. Crystal and molecular structures of 1β, 1py*, 2MeOH, 2EtOH, 2py, 3 and 3MeOH were determined by the single crystal X-ray diffraction method. All complexes were characterized by microanalysis, FT- IR and CW-EPR spectroscopy, thermogravimetric analysis and powder X-ray diffraction method.

synthetic methods ; nuclearity and geometry ; copper(II) complexes ; aroylhydrazones

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